JP2010204568A - Electrophotographic toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner and toner kit which has a wide color reproduction range, permits adjustment of chroma/glossiness, can form a pictorial image and is excellent in weatherability and gas-barrier property, and to provide an image forming method and image forming apparatus using the toner and toner kit. <P>SOLUTION: The colorless transparent toner includes at least a binder resin and a lamellar inorganic mineral, wherein the lamellar inorganic mineral is an organic modified lamellar inorganic mineral in which at least a part of ions between layers are modified with organic ions. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic image used in a copying machine, a printer or the like to which an electrophotographic technique is applied, an image forming apparatus using the toner, a container containing toner, and a process cartridge.

In electrophotographic image formation, it is necessary to expand the color reproduction range to enable the formation of pictorial images, and attempts to ensure color reproducibility by using color toners that use dyes instead of pigments Has been done.
In order to adjust saturation and gloss, color toner and transparent toner are used in combination, and the transparent toner is superimposed on the color toner.

Patent Document 1 proposes to use a transparent toner having a viscosity of 80 to 130 ° C. at which the viscosity becomes 10 ³ Pa · s and a colored toner having a viscosity close to the viscosity of the transparent toner. Is set so that the storage elastic modulus at the temperature reached in the fixing nip of the white toner or the transparent toner at the fixing step is higher than the storage elastic modulus at the temperature reached in the fixing nip of each color toner at the fixing step. Further, it is proposed to use a color toner and a colorless adhesive toner exhibiting a glass transition temperature lower than that of the color toner.
However, these methods can give gloss, but there is a problem that the weather resistance is poor even if the transparent toner is overcoated.

The present invention provides a toner, a toner kit, an image forming method using the same, an image forming method, and an image forming method, capable of forming a pictorial image with a wide color reproduction range, adjustable saturation and gloss, and excellent in weather resistance and gas barrier properties. An object is to provide an apparatus.

The present invention is solved by the following (1) to (7).
(1) A colorless transparent toner containing at least a binder resin and a layered inorganic mineral, wherein the layered inorganic mineral is an organically modified layered inorganic mineral in which at least some of the ions between layers are modified with organic ions. A colorless transparent toner.
(2) The colorless and transparent toner as described in (1) above, wherein the content of the layered inorganic mineral is 0.01 wt% or more and 20 wt% or less.
(3) A toner kit including a colored toner and a colorless transparent toner,
The colored toner includes at least a binder resin and a colorant, and the colorless and transparent toner is the colorless and transparent toner according to the item (1) or (2). .
(4) The toner kit according to item (3), wherein the colorant of the colored toner is a dye.
(5) A toner kit having a plurality of developer containers, a developer supply member that supplies developer from the developer containers of the toner kit to the surface of the developer carrier, and the supplied developer on the surface A developing device having a developer carrier,
The developing device, wherein the toner kit is the toner kit according to the item (3) or the item (4).
(6) In an image forming apparatus having at least a toner image forming unit for forming a color toner image and a colorless transparent toner image on a recording medium and a fixing unit for fixing the toner image on the recording medium to the recording medium.
A latent image carrier on which the toner image forming means carries a latent image;
Charging means for uniformly charging the surface of the latent image carrier;
Exposure means for exposing the surface of the charged latent image carrier on the basis of image data and writing an electrostatic latent image;
A developing device that supplies toner to the electrostatic latent image formed on the surface of the latent image carrier to visualize it;
Transfer means for transferring a visible image on the surface of the latent image carrier to a recording medium;
An image forming apparatus comprising the developing device according to item (5) as the developing device.
(7) At least a toner image forming step for forming an image made of colored toner and an image made of a colorless transparent toner on the recording medium, and fixing for fixing the toner image on the recording medium formed in the toner image forming step to the recording medium An image forming method comprising: using the toner kit according to item (3) or (4) as a toner.

  According to the present invention, the organically modified layered inorganic mineral modified with organic ions has a layered clay crystal having a thickness of about 1 nm and is densely stacked in the same direction, and therefore has a gas barrier property due to a detour effect. Even in the case of color toners that use high color fading materials such as dyes as the color material, overcoating can prevent fading, improve weather resistance, and color reproduction of pictorial images Therefore, it is possible to provide a toner and an image forming apparatus capable of obtaining a printed matter having excellent weather resistance while maintaining the properties.

1 is a cross-sectional view of a main part of an image forming apparatus including a developing device and a process cartridge unit according to the present invention. FIG. 2 is a cross-sectional view of a developing device and a process cartridge unit according to the present invention.

  The present invention has been made in view of the above problems, and the toner of the present invention includes a colorless resin containing at least a binder resin and an organically modified layered inorganic mineral in which at least part of ions between layers is modified with organic ions. Transparent toner.

Below, each component which comprises the toner of this invention is demonstrated.
<Modified layered inorganic mineral>
The layered inorganic mineral is an inorganic mineral made up of several nm thick layers, and the crystal structure is a stack of three layers: silicate tetrahedral layer-alumina octahedral layer-silicate tetrahedral layer The unit layer has a very thin plate shape with a thickness of about 1 nm and a spread of 0.1 to 1 μm.
In the layered inorganic mineral, layered clay crystals having a thickness of about 1 nm are densely stacked by being oriented in the same direction, and thus the gas barrier property is improved by the detour effect.
Denaturing means introducing organic ions into the ions present between the layers. This is called intercalation in a broad sense.
The organically modified layered inorganic mineral in the present invention is one in which at least part of ions between layers of the layered inorganic mineral is modified with organic ions.

  As the layered inorganic mineral, smectite group (montmorillonite, saponite, etc.), kaolin group (kaolinite, etc.), magadiite, and kanemite can be used. The layered inorganic mineral is highly hydrophilic due to ions between layers. Therefore, if the layered inorganic mineral is dispersed in an aqueous medium without being modified with organic ions and the toner is granulated, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed. By modifying with ions, it is easily deformed during granulation, dispersed and refined, and exhibits a sufficient charge adjustment function. At this time, the content of the organically modified layered inorganic mineral in the toner material is preferably 0.01 wt% or more and 20 wt% or less, more preferably 0.5 wt% or more and 10 wt% or less, and 4.5 wt% or more and 5 wt% or less. More preferably, it is 5 wt% or less. When the content is 0.01 wt% or less, the gas barrier property cannot be exhibited, and when it exceeds 20.0 wt%, the concentration and the saturation decrease.

The layered inorganic mineral modified with organic ions used in the present invention is preferably one having a smectite-based basic crystal structure modified with an organic cation.
Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal.
However, since a layered inorganic mineral into which a metal anion is introduced has high hydrophilicity, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.

Examples of the organic ion modifier that modifies at least a part of the ions of the layered inorganic mineral include quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts, and the like, but quaternary alkyl ammonium salts are desirable. . Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.
Examples of the organic ion modifier include branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, and the like. Sulfates, sulfonates, carboxylates or phosphates are raised. A carboxylic acid having an ethylene oxide skeleton is desirable.

The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable.
Commercially available layered inorganic minerals partially modified with organic cations include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL (above, Quartium 18 bentonite such as Southern Clay, Inc .; Steallarconium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (above, produced by Southern Clay), etc .; Clayton HT And quaternium 18 / benzalkonium bentonite such as Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. Moreover, as a layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable. As what modified | denatured with the organic anion represented by following General formula (1), for example, Hytenol 330T (made by Daiichi Kogyo Seiyaku Co., Ltd.) is mentioned.

General formula (1) R1 (OR2) nOSO ₃ M
[Wherein R 1 represents an alkyl group having 13 carbon atoms, and R 2 represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element]

  A kneaded composite of the modified layered inorganic mineral and the binder resin, that is, a master batch is obtained by mixing and kneading the binder resin and the layered inorganic mineral modified with organic ions under high shear force to obtain a master batch. it can. In this case, an organic solvent can be used to enhance the interaction between the modified layered inorganic mineral and the binder resin. Also, a so-called flushing method is a method in which an aqueous paste containing the modified layered inorganic mineral and water is mixed and kneaded together with a resin and an organic solvent, and the modified layered inorganic mineral is transferred to the resin side to remove moisture and organic solvent components. Also, since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

  In the kneaded composite of the modified layered inorganic mineral and the binder resin, that is, the master batch, the volume average particle diameter Dv of the modified layered inorganic mineral is preferably 0.1 μm or more and 0.5 μm or less. When the volume average particle diameter Dv is less than 0.1 μm, the gas barrier effect is not sufficient, and when it exceeds 0.5 μm, the dispersibility in the toner is poor and the gas barrier effect cannot be exhibited.

<Resin binder resin for toner>
(Binding resin for pulverized toner)
As the binder resin for toner, a resin containing a first binder resin and a second binder resin can be used.
The type of the first binder resin and the second binder resin is not particularly limited, and is a binder resin known in the field of full-color toner, for example, polyester resin, (meth) acrylic resin, styrene- (meth) acrylic resin. It may be a copolymer resin, an epoxy resin, COC (cyclic olefin resin, for example, TOPAS-COC (manufactured by Ticona)), etc., but from the viewpoint of oilless fixing, the first binder resin and the second binder resin In any case, it is preferable to use a polyester resin.

  As the polyester resin preferably used in the present invention, a polyester resin obtained by polycondensation of a polyhydric alcohol component and a polyvalent carboxylic acid component can be used. Among the polyhydric alcohol components, examples of the dihydric alcohol component include polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3,3) -2,2- Bis (4-hydroxyphenyl) propane, polyospropylene (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane Bisphenol A alkylene oxide adducts such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, and the like. Examples of the trihydric or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Is mentioned.

Among the polyvalent carboxylic acid components, examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, and succinic acid. , Adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, isooctenyl succinic acid, n-octyl succinic acid , Isooctyl succinic acid, anhydrides or lower alkyl esters of these acids.
Examples of the trivalent or higher carboxylic acid component include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2 , 4-Naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4- Examples include cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, anhydrides of these acids, and lower alkyl esters.

In the present invention, as a polyester resin, a polyester resin raw material monomer, a vinyl resin raw material monomer, and a mixture of monomers that react with both resin raw material monomers are used to obtain a polyester resin in the same container. A resin obtained by performing a condensation polymerization reaction and a radical polymerization reaction for obtaining a vinyl resin in parallel (hereinafter, simply referred to as “vinyl polyester resin”) can also be suitably used. In addition, the monomer which reacts with the raw material monomers of both resins is, in other words, a monomer that can be used for both the condensation polymerization reaction and the radical polymerization reaction. That is, it is a monomer having a carboxy group that can undergo a condensation polymerization reaction and a vinyl group that can undergo a radical polymerization reaction, and examples thereof include fumaric acid, maleic acid, acrylic acid, and methacrylic acid.
Examples of the raw material monomer for the polyester resin include the above-described polyhydric alcohol component and polyvalent carboxylic acid component. Examples of the raw material monomer for the vinyl resin include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert- Styrene or styrene derivatives such as butylstyrene and p-chlorostyrene; Ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate , Isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, neopentyl methacrylate, 3- (methyl) butyl methacrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate Methacrylic acid alkyl esters such as decyl methacrylate, undecyl methacrylate, dodecyl methacrylate; methyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, acrylic Alkyl acrylates such as n-pentyl acid, isopentyl acrylate, neopentyl acrylate, 3- (methyl) butyl acrylate, hexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, and dodecyl acrylate Esters; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid; acrylonitrile, maleic acid ester, itaconic acid ester, vinyl chloride, vinyl acetate, vinyl benzoate, vinylmethyl Examples include ethyl ketone, vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether. As a polymerization initiator when polymerizing the raw material monomer of the vinyl resin, for example, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1 Azo or diazo polymerization initiators such as' -azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, benzoyl peroxide, dicumyl peroxide, And peroxide polymerization initiators such as methyl ethyl ketone peroxide, isopropyl peroxycarbonate, lauroyl peroxide, and the like.

As the first binder resin and the second binder resin, various polyester resins as described above are preferably used. Among them, from the viewpoint of further improving the separation property and the offset resistance as the oilless fixing toner, It is more preferable to use the following first and second binder resins.
A more preferred first binder resin is a polyester resin obtained by polycondensation of the above-mentioned polyhydric alcohol component and polyhydric carboxylic acid component, particularly a bisphenol A alkylene oxide adduct as the polyhydric alcohol component. It is a polyester resin obtained using terephthalic acid and fumaric acid as the acid component.
More preferred second binder resins are vinyl polyester resins, particularly bisphenol A alkylene oxide adduct, terephthalic acid, trimellitic acid and succinic acid are used as raw material monomers for polyester resins, and styrene and butyl acrylate are used as raw material monomers for vinyl resins. And a vinyl-based polyester resin obtained using fumaric acid as a bireactive monomer.

In the present invention, as described above, a hydrocarbon release agent is internally added during the synthesis of the first binder resin. In order to add a hydrocarbon-based release agent to the first binder resin in advance, when synthesizing the first binder resin, a hydrocarbon-based release agent is included in the monomer for synthesizing the first binder resin. The first binder resin may be synthesized in a state where is added. For example, the polycondensation reaction may be performed in a state where a hydrocarbon-based release agent is added to the acid monomer and the alcohol monomer constituting the polyester resin as the first binder resin. When the first binder resin is a vinyl polyester resin, a vinyl resin raw material monomer is added to the polyester resin raw material monomer while stirring and heating the hydrocarbon release agent. May be added dropwise to conduct a polycondensation reaction and a radical polymerization reaction.

(Resin binder resin for polymerized toner)
The resin binder resin for polymerized toner (A) used in the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. Particularly, styrene-acrylic resins, polyester resins, etc. Preferably mentioned.
In the present invention, a polyester resin is particularly preferably used, and the type is not particularly limited, and any type can be used, and several types of polyester resins may be mixed and used. Examples of the polyester resin include polycondensates of the following polyol (1) and polycarboxylic acid (2).

(About polyol)
Examples of the polyol (1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyls such as bisphenol S, 3,3′-difluoro-4,4′-dihydroxybiphenyl, etc .; bis (3-fluoro-4-hydroxyphenyl) Nyl) methane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3 Bis (5-difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol A), 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, etc. Hydroxyphenyl) alkanes; bis (4-hydroxyphenyl) ethers such as bis (3-fluoro-4-hydroxyphenyl) ether); alkylene oxides of the above alicyclic diols (ethylene oxide, propylene oxide, butylene oxide, etc.) Adducts; alkylene oxides of the above bisphenols (ethylene oxide) De, propylene oxide, and the like butylene oxide, etc.) adducts.
Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.
In addition, trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol PA, phenol novolac, cresol novolac, etc.) ); Alkylene oxide adducts of the above trihydric or higher polyphenols.
In addition, the said polyol can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

(Polycarboxylic acid)
Examples of the polycarboxylic acid (2) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, Naphthalenedicarboxylic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5- Trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoropropane 2,2′-bis (trifluoromethyl) -4,4′- Phenyldicarboxylic acid, 3,3′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 2,2′-bis (trifluoromethyl) -3,3′-biphenyldicarboxylic acid, hexafluoroisopropylidene Dendiphthalic anhydride, etc.).
Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Further, polyvalent polycarboxylic acids having 3 or more valences are aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and acid anhydrides or lower alkyl esters (methyl esters, ethyl esters) described above. , Isopropyl ester, etc.) may be used to react with polyol (1). In addition, the said polycarboxylic acid can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.
(Ratio of polyol and polycarboxylic acid)
The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

(Molecular weight of polyester resin)
The peak molecular weight is usually 1000 to 30000, preferably 1500 to 10000, more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 30000, low-temperature fixability will deteriorate.

<Modified polyester resin>
The binder resin (A) used in the present invention may contain a modified polyester resin having a urethane or / and urea group in order to adjust viscoelasticity for the purpose of preventing offset. In the binder resin (A), the content of the modified polyester resin having urethane or / and urea groups is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. When the content ratio exceeds 20%, the low-temperature fixability is deteriorated. The modified polyester resin having a urethane or / and urea group may be directly mixed with the binder resin (A), but from the viewpoint of productivity, a relatively low molecular weight modified polyester having an isocyanate group at the terminal. A resin (hereinafter sometimes referred to as a prepolymer) and an amine that reacts with the resin are mixed with the binder resin (A), and during the granulation / after granulation, chain elongation or / and a crosslinking reaction are carried out to produce the urethane. Alternatively, it is preferable to become a modified polyester resin having a urea group. By doing so, it becomes easy to contain a relatively high molecular weight modified polyester resin for adjusting the viscoelasticity in the core portion.

(Prepolymer)
Examples of the prepolymer having an isocyanate group include a polycondensate of the polyol (1) and the polycarboxylic acid (2) and a polyester having an active hydrogen group that is further reacted with a polyisocyanate (3). . Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

(Polyisocyanate)
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

(Ratio of isocyanate group to hydroxyl group)
The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1.
When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the offset resistance deteriorates. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

(Number of isocyanate groups in the prepolymer)
The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. When the number is less than 1 per molecule, the molecular weight of the modified polyester after chain extension and / or crosslinking becomes low, and offset resistance deteriorates.

(Chain extension and / or cross-linking agent)
In the present invention, amines can be used as chain extenders and / or crosslinkers. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned.
Examples of the diamine (B1) include the following.
Aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine, etc.);
Alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc.);
And aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluorododecylenediamine, etc.) Examples of the trivalent or higher polyamine (B2) include diethylenetriamine, triethylenetetramine, and the like. It is done.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

(Stopper)
Furthermore, the molecular weight of the modified polyester after completion of the reaction can be adjusted by using a terminator for the chain extension and / or crosslinking reaction, if necessary. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).

(Ratio of amino group to isocyanate group)
The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

<Colorant>
As the coloring agent of the present invention, all known dyes and pigments can be used, and as the pigment-based coloring agent, carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, magnetic ferrite, magnetite, yellow lead, zinc Yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, hanzer yellow G, hanzer yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG , Tartrazine lake, red chrome yellow, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, Indanthrene Brilliant Orange RK, Benzidine Orange G, Indanthren Brilli Orange GK, Bengala, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, risor red, pyrazolone red, watching red, calcium salt, lake red C, lake red D, brilliant carmine 6B, Eoxy lake, rhodamine lake B , Alizarin lake, brilliant carmine 3B and the like.
Manganese purple, Fast violet R, Methyl violet lake, Bitumen, Cobalt blue, Alkaline blue lake, Victoria blue lake, Phthalocyanine blue, Metal-free phthalocyanine blue, Phthalocyanine blue partially chlorinated, Fast sky blue, Induslen blue BC .
Solvent yellow 9, 17, 24, 31, 35, 58, 93, 100, 102, 103, 105, 112, 162, 163, disperse yellow 3, 42, 64, 82, 160, 201 as dye colorants , C.I. I. Disperse violet 26, 31, C.I. I. Disperse thread 4, 5, 60, 91, C.I. I. Solvent Red 8, 49, 52, BASF Neopen Magenta 525, Bayer Macrolex RED H, Solvent Blue 36, 63, 64, 67, 68, 70, 97, BASF Neopen Cyan742, Bayer Macrolex Blue3, etc. can give.
The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

<Colorant master batch>
The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

<Master batch production method>
This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of colorant is mixed and kneaded with resin and organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

<Release agent>
As the release agent used in the present invention, known ones can be used, for example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. Can be mentioned. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, 18-octadecanediol distearate etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide etc.); polyalkylamides (trimellitic acid tristearyl amide etc.) ); And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.
In the present invention, it is more preferable that the wax content in the toner is 5 to 15% by weight with respect to 100% by weight of the resin component. If the amount of wax with respect to the total amount of toner is less than 5%, the releasing effect by the wax may be lost, and the margin for preventing offset may be lost. On the other hand, if it exceeds 15%, the wax melts at a low temperature, so it is easily affected by thermal energy and mechanical energy. It may adhere to the image carrier and generate image noise. Further, the endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the wax can fix the toner at a low temperature of 65 to 115 ° C., but if the melting point is less than 65 ° C., the fluidity becomes poor. When the temperature is higher than 115 ° C., the fixability tends to deteriorate.

<Charge control agent>
The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

<External additive>
(Inorganic fine particles)
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium zinc titanate, tin oxide, quartz sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, composite oxides such as silicon oxide / magnesium oxide and silicon oxide / aluminum oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride And so on.
(Polymer fine particles)
In addition, polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine and nylon, and thermosetting resin Examples include polymer particles.

(Surface treatment of external additives)
Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

(Cleaning aid)
Examples of the cleaning property improving agent for removing the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, such as polymethyl methacrylate fine particles. And polymer fine particles produced by soap-free emulsion polymerization such as polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

<Toner production method>
When the toner material is emulsified or dispersed in the aqueous medium using the liquid containing the toner material, the liquid containing the toner material is preferably dispersed in the aqueous medium while stirring.
A known disperser or the like can be appropriately used for the dispersion. Specific examples of the disperser include a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, and an ultrasonic disperser. Especially, since the particle diameter of a dispersion (oil droplet) can be controlled to 2-20 micrometers, a high-speed shearing disperser is preferable.
When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The rotation speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 0 to 150 ° C. and more preferably 40 to 98 ° C. under pressure. In general, the dispersion is easier when the dispersion temperature is higher.

The method for forming the toner base particles can be appropriately selected from known methods. Specifically, a method for forming toner base particles using a suspension polymerization method, an emulsion polymerization aggregation method, a dissolution suspension method, or the like, a method for forming toner base particles while producing an adhesive substrate, etc. Among these, a method of forming toner base particles while producing an adhesive substrate is preferable. Here, the adhesive base material is a base material having adhesiveness to a recording medium such as paper.
A method of forming toner base particles while producing an adhesive substrate is a method in which a toner material contains a compound having an active hydrogen group and a polymer having reactivity to the active hydrogen group, and is active in an aqueous medium. This is a method of forming toner base particles while producing an adhesive substrate by reacting a compound having a hydrogen group with a polymer having reactivity with an active hydrogen group.
In addition, the adhesive base material may further contain a known binder resin.
The toner thus obtained preferably contains a colorant, and may further contain other components such as a release agent and a charge control agent that are appropriately selected as necessary.
The weight average molecular weight of the adhesive substrate is preferably 3000 or more, more preferably 5000 to 1000000, and particularly preferably 7000 to 500000. When the weight average molecular weight is less than 3000, the hot offset resistance may be lowered.

The production method of the toner of the present invention is not limited to this, but is preferably produced by the following production method.
The method for producing the toner of the present invention comprises dissolving or dispersing a binder resin, a highly polar resin, a colorant and a release agent having at least an aromatic group-containing polyester skeleton in an organic solvent, and then dissolving or dispersing the binder or resin. At least a step of dispersing in an aqueous medium and granulating.
More specifically, it is as follows.

<Granulation process>
(Organic solvent)
As an organic solvent for dissolving or dispersing a binder resin having an aromatic group-containing polyester skeleton, a colorant and a release agent, the Hansen solubility parameter described in Volume 2, Section VII of “POLYMER HANDBOOK” 4th Edition, WILEY-INTERSCIENCE What becomes 19.5 or less is preferable, and it is preferable that the boiling point is less than 100 ° C. from the viewpoint of easy removal of the solvent later. Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. Particularly preferred are ester solvents such as methyl acetate and ethyl acetate, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride. The polyester resin, the colorant and the release agent may be dissolved or dispersed at the same time. Usually, each of them is dissolved or dispersed alone, and the organic solvents used at that time may be different or the same. The same is preferable considering the above.

(Dissolution or dispersion of binder resin having aromatic group-containing polyester skeleton)
The resin concentration or concentration of the binder resin having an aromatic group-containing polyester skeleton is preferably about 40% to 80%. If the concentration is too high, it will be difficult to dissolve or disperse, and the viscosity will be too high to handle. On the other hand, if the density is too low, the amount of toner produced decreases. When mixing a modified polyester resin having an isocyanate group at the terminal with a binder resin having an aromatic group-containing polyester skeleton, it may be mixed in the same solution or dispersion, or separately prepared in a solution or dispersion. However, considering the respective solubility and viscosity, it is preferable to prepare separate solutions or dispersions.

(Dissolution or dispersion of colorant)
The colorant may be dissolved or dispersed alone, or may be mixed in the solution or dispersion of the polyester resin. If necessary, a dispersion aid or a polyester resin may be added, or the master batch may be used.

(Dissolution or dispersion of release agent)
When dissolving or dispersing wax as a release agent, when using an organic solvent in which wax does not dissolve, it is used as a dispersion, but the dispersion is prepared by a general method. That is, an organic solvent and wax may be mixed and dispersed with a disperser such as a bead mill. Further, after mixing the organic solvent and the wax, it is sometimes possible to shorten the dispersion time by once heating to the melting point of the wax, cooling with stirring and then dispersing with a disperser such as a bead mill. In addition, a plurality of waxes may be mixed and used, or a dispersion aid or a polyester resin may be added.

(Dispersion of modified layered inorganic minerals)
The modified layered inorganic mineral can be mixed in the binder resin solution or dispersion.
Further, the modified layered inorganic mineral and the binder resin may be mixed, melt-kneaded and then pulverized, and used as a kneaded composite (master batch) of the modified layered inorganic mineral and the binder resin.

(Aqueous medium)
As an aqueous medium to be used, water alone may be used, but a solvent miscible with water may be used in combination. Furthermore, an organic solvent having a Hansen solubility parameter of 19.5 or less used in the oil phase may be mixed, and preferably the addition amount in the vicinity of the saturation amount with respect to water increases the emulsification or dispersion stability of the oil phase. it can. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like. The amount of the aqueous medium used relative to 100 parts by mass of the toner composition is usually 50 to 2000 parts by mass, preferably 100 to 1000 parts by mass. If the amount is less than 50 parts by mass, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle size cannot be obtained. Moreover, when it exceeds 2000 mass parts, it is not economical.

(Inorganic dispersant and organic resin fine particles)
When the dissolved or dispersed toner composition is dispersed in the aqueous medium, by dispersing the inorganic dispersant or the organic resin fine particles in the aqueous medium in advance, the particle size distribution is sharpened and the dispersion is reduced. It is preferable in terms of stability. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used. As the resin for forming the organic resin fine particles, any resin that can form an aqueous dispersion can be used, and it may be a thermoplastic resin or a thermosetting resin. Includes vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like. Two or more of these resins may be used in combination. Among these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferable from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained.

(Method for dispersing organic resin fine particles in water)
The method of making the resin into an aqueous dispersion of fine organic resin particles is not particularly limited, and examples thereof include the following (a) to (h).
(A) In the case of a vinyl resin, a method of directly producing an aqueous dispersion of resin fine particles by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method using a monomer as a starting material .
(B) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof is dispersed in an aqueous medium in the presence of a suitable dispersant, A method of producing an aqueous dispersion of resin fine particles by heating and then adding a curing agent to cure.
(C) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, and epoxy resin, a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably liquid) may be liquefied by heating. .) A method in which a suitable emulsifier is dissolved therein, and then water is added to perform phase inversion emulsification.
(D) A resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) can be used as a mechanical rotary type or jet type resin. A method in which resin fine particles are obtained by pulverization using a fine pulverizer and then classification, and then dispersed in water in the presence of an appropriate dispersant.
(E) A resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, A method in which resin fine particles are obtained by spraying in the form of a mist and then dispersed in water in the presence of an appropriate dispersant.
(F) A solvent is added to a resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. The resin fine particles are precipitated by cooling the resin solution previously dissolved in a solvent by heating, and then the solvent is removed to obtain resin fine particles, which are then dispersed in water in the presence of a suitable dispersant. Method.
(G) A resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, A method of dispersing in an aqueous medium in the presence of an appropriate dispersant and removing the solvent by heating or decompression.
(H) In a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. A method of phase inversion emulsification by adding water after dissolving an appropriate emulsifier.

(Surfactant)
Further, a surfactant or the like can be used as necessary in order to emulsify and disperse the oily phase containing the toner composition in the aqueous medium. As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. It is.
Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms, and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6 -C11) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) ) Carboxylic acid and metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic acid diethanolamide, N-propyl-N -(2-hydroxyethyl) par Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned. In addition, examples of the cationic surfactant include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

(Protective colloid)
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Of methyl alcohol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole , Homopolymers or copolymers such as those having a nitrogen atom such as ethyleneimine or its heterocyclic ring, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.
In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation. When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable from the charged surface of the toner to be removed by washing.

(Distribution method)
The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

(Solvent removal)
In order to remove the organic solvent from the obtained emulsified dispersion, a known method can be used. For example, it is possible to employ a method in which the entire system is gradually heated under normal pressure or reduced pressure to completely evaporate and remove the organic solvent in the droplets.

<Extension or / and cross-linking reaction>
For the purpose of introducing a modified polyester resin having a urethane or / and urea group, when adding a modified polyester resin having an isocyanate group at the terminal and an amine capable of reacting with it, the toner composition is added to an aqueous medium. Before dispersion, amines may be mixed in the oil phase, or amines may be added to the aqueous medium. The time required for the above reaction is selected depending on the reactivity of the isocyanate group structure of the polyester prepolymer and the added amines, but is usually 1 minute to 40 hours, preferably 1 to 24 hours. The reaction temperature is usually
It is 0-150 degreeC, Preferably it is 20-98 degreeC. This reaction may be performed before the fine particle adhesion step, or may be performed simultaneously during the fine particle adhesion step. Further, it may be after the fine particle adhesion step is completed. Moreover, a well-known catalyst can be used as needed.

<Washing and drying process>
A known technique is used for the step of washing and drying the toner particles dispersed in the aqueous medium.
That is, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion exchange water at about room temperature to about 40 ° C., and after adjusting the pH with acid or alkali as necessary, After removing the impurities and surfactants by repeating the process of solid-liquid separation again and again, the toner powder is obtained by drying with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. . At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

<External processing>
The obtained dried toner powder is mixed with different particles such as the charge control fine particles and fluidizing agent fine particles, or fixed and fused on the surface by applying mechanical impact force to the mixed powder. It is possible to prevent the dissociation of the foreign particles from the surface of the resulting composite particle. Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. Henschel mixer (made by Mitsui Mining Co., Ltd.), super mixer (made by Kawata Co., Ltd.), Ong mill (made by Hosokawa Micron Co., Ltd.) and I-type mill (made by Nippon Pneumatic Co., Ltd.) were modified to reduce the pulverization air pressure. Examples thereof include an apparatus, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

<Charging imparting member>
In consideration of toner adhesion, the charge imparting member for recharging the toner remaining on the surface of the electrostatic latent image holding member after transfer from the electrostatic latent image bearing member to the next process is attached due to charge-up if it is insulative. In order to generate, it is preferable that it is electroconductive. The surface resistance is preferably 102-8 Ω / sq, and the volume resistance is preferably 101-6 Ω / sq.
Further, examples of the shape include a roller, a brush, a sheet, and the like, and more preferably, a sheet configuration is preferable in consideration of resetting property of attached toner.
The electricity imparting member is preferably a sheet selected from nylon, PTFE, PVDF, and urethane, and more preferably PTFE or PVDF from the viewpoint of toner chargeability.
When the charge imparting member is a conductive sheet, the thickness is preferably 0.05 to 0.5 mm from the viewpoint of the contact pressure with the electrostatic latent image carrier.
When the charge imparting member is a conductive sheet, the nip width in contact with the latent image carrier is preferably 1 to 10 mm from the viewpoint of contact time when toner is charged.
The voltage applied to the charge imparting member is preferably −1.4 kv to 0 kV from the viewpoint of imparting toner charge.
Toner analysis and evaluation were performed as follows. Although the following was evaluated as a one-component developer, the toner of the present invention can also be used as a two-component developer by using a suitable external addition process and a suitable carrier.

The constituent features of the present invention will be described below.
(Developer, process cartridge)
FIG. 1 is a cross-sectional view of a main part of an image forming apparatus including a developing device and a process cartridge unit according to an embodiment of the present invention.
Each process cartridge unit (201) has a structure in which a photosensitive drum (202), a charging roller (203), a developing device (204), and a cleaning means (205) are integrally coupled. Each process cartridge unit (201) is configured to be replaceable by releasing each stopper.
The photosensitive drum (202) rotates in the direction of the arrow at a peripheral speed of 150 mm / sec.
The charging roller (203) is in pressure contact with the surface of the photosensitive drum (202), and is rotated by the rotation of the photosensitive drum (202). A predetermined bias is applied to the charging roller (203) by a high voltage power source (not shown), and the surface of the photosensitive drum (202) is charged to -500V.
The exposure means (206) exposes image information to the photosensitive drum (202) to form an electrostatic latent image. A laser beam scanner or LED using a laser diode is used for this exposure means (206).
The developing device (204) is one-component contact development, and visualizes the electrostatic latent image on the photosensitive drum (202) as a toner image. A predetermined developing bias is supplied to the developing device (204) from a high voltage power source (not shown).
The photoconductor cleaning means (205) cleans the transfer residual toner on the surface of the photoconductor drum (202).

Each process cartridge unit (201) is arranged in parallel in the moving direction of the intermediate transfer belt (207). For example, colorless transparent resin particles are stored in the uppermost developing device (204), and the other four cartridges. In the developing device (204), toners are stored in the order of yellow, cyan, magenta, and black to form a visible image. A primary transfer bias is applied to the primary transfer roller (208), and the toner image on the surface of the photosensitive drum (202) is transferred to the surface of the intermediate transfer belt (207). The intermediate transfer belt (207) is driven to rotate in the direction of the arrow in the figure by a drive motor (not shown), and a full color image is formed by sequentially transferring the visible images of each color onto the surface.
The formed full color image is transferred to a sheet (210) as a transfer material by applying a predetermined voltage to the secondary transfer roller (209), and is fixed and output by a fixing device (not shown). The toner that cannot be transferred by the secondary transfer roller (209) and remains on the intermediate transfer belt (207) is collected by the transfer belt cleaning means (211).

  The developing device of the present invention has a plurality of developer containers, and stores colorless and transparent resin particles in at least one of them. The developing device of the present invention includes a developer supply member that supplies developer from the developer container to the surface of the developer carrier, and a developer carrier that supports the supplied developer on the surface. Yes. The developer container can be composed of at least a developer container that stores colored toner and a developer container that stores at least colorless and transparent resin particles.

FIG. 2 is a sectional view of the developing device and the process cartridge unit according to the embodiment of the present invention.
The developing device (204) includes a toner storage chamber (101) that stores toner (100) and a toner supply chamber (102) provided below the toner storage chamber (101). The toner supply chamber (102) A developing roller (103), a layer regulating member (104) provided in contact with the developing roller (103), and a supply roller (105) are provided at a lower portion of the roller. The developing roller (103) is disposed in contact with the photosensitive drum (202), and a predetermined developing bias is applied from a high voltage power source (not shown).

A toner stirring member (106) is provided in the toner storage chamber (101), and the stored toner flows by rotating in a counterclockwise direction. The toner supply chamber (102) passes through the opening (107). ) To promote falling movement to. The opening (107) is provided immediately above the supply roller, and only a wall for partitioning the toner storage chamber (101) and the toner supply chamber 102 is provided immediately above the layer regulating member (104). The surface of the supply roller (105) is covered with a foam material having a structure having pores (cells), and the toner conveyed into the toner supply chamber (102) is efficiently attached and taken in, and developed. Toner deterioration due to pressure concentration at the contact portion with the roller (103) is prevented. In addition, a conductive material containing carbon fine particles is used as the foam material, and the electric resistance value is set to 10 ³ to 10 ¹³ Ω. A supply bias having a value offset in the same direction as the toner charging polarity with respect to the developing bias is applied to the supply roller (105). The supply bias acts in a direction in which the toner preliminarily charged at the contact portion with the developing roller (103) is pressed against the developing roller (103). The supply roller (105) rotates counterclockwise to apply and supply the toner adhered to the surface to the surface of the developing roller (103).

A roller coated with an elastic rubber layer is used for the developing roller (103), and a surface coat layer made of a material that is easily charged to a polarity opposite to that of the toner is provided on the surface. The elastic rubber layer is set to a hardness of 60 degrees or less in accordance with JIS-A in order to keep the contact state with the photosensitive drum (202) uniform, and further 10 ³ to 10 ¹⁰ Ω in order to act a developing bias. Set to electrical resistance value. The surface roughness Ra is set to 0.3 to 2.0 μm, and a necessary amount of toner is held on the surface. The developing roller (103) rotates counterclockwise and conveys the toner held on the surface to a position facing the layer regulating member (104) and the photosensitive drum (202).
The layer regulating member is provided at a position lower than the contact position between the supply roller and the developing roller (103). The layer regulating member uses a metal leaf spring material such as SUS or phosphor bronze, and the free end is brought into contact with the surface of the developing roller (103) with a pressing force of 10 to 40 N / m, and passes under the pressure. The toner is thinned and charged by triboelectric charging. Further, a regulation bias having a value offset in the same direction as the toner charging polarity with respect to the developing bias is applied to the layer regulating member in order to assist frictional charging.

The rubber elastic body constituting the surface of the developing roller is not particularly limited. For example, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylic rubber, epichlorohydrin rubber, urethane rubber, silicon rubber, These 2 or more types of blends etc. are mentioned. Among these, a blend rubber of epichlorohydrin rubber and acrylonitrile-butadiene copolymer rubber is preferably used.
The developing roller used in the present invention is manufactured, for example, by covering the outer periphery of a conductive shaft with a rubber elastic body. The conductive shaft is made of a metal such as stainless steel, for example.

The photosensitive drum (202) rotates in the clockwise direction, and therefore the surface of the developing roller (103) moves in the same direction as the traveling direction of the photosensitive drum (202) at a position facing the photosensitive drum (202). To do.
The thinned toner is conveyed to a position facing the photosensitive drum (202) by the rotation of the developing roller (103), and the developing bias applied to the developing roller (103) and the photosensitive drum (202). In accordance with the latent image electric field formed by the electrostatic latent image, it moves to the surface of the photosensitive drum (202) and is developed.
A seal (108) is attached to the developing roller (103) at a portion where the toner remaining on the developing roller (103) without being developed on the photosensitive drum (202) returns to the toner supply chamber (102) again. The toner is sealed so as not to leak out of the developing device.

The configuration of the electrostatic latent image carrier charging member will be described.
The charging member of the present invention includes a cored bar, a conductive layer on the cored bar, and a surface layer covering the conductive layer, and is formed in a cylindrical shape as a whole. A voltage applied to the core metal by the power source is applied to the core metal through the conductive layer and the surface layer to the photosensitive drum (202) to charge the surface of the photosensitive drum (202).
The core of the charging member is disposed along the longitudinal direction of the photosensitive drum (202) (parallel to the axis of the photosensitive drum (202)), and the entire charging member is disposed with respect to the photosensitive drum (202). And pressed with a predetermined pressing force. As a result, a part of the surface of the photosensitive drum (202) and a part of the surface of the charging member are in contact with each other along the longitudinal direction thereof to form a contact nip having a predetermined width. The photosensitive drum (202) is rotationally driven by a driving means (not shown), and the charging member is configured to be driven and rotated accordingly.
The photosensitive drum (202) is charged by the power source through the vicinity of the contact nip. Through the contact nip, the surface of the charging member and the charged region (corresponding to the length of the charging member) on the surface of the photosensitive drum (202) are in contact with each other. The charged area is uniform.

The conductive layer of the charging member is non-metallic, and a low hardness material can be preferably used in order to stabilize the contact state with the photosensitive drum (202). For example, resins such as polyurethane, polyether, and polyvinyl alcohol, and rubbers such as hydrin, EPDM, and NBR are used. Examples of the conductive material include carbon black, graphite, titanium oxide, and zinc oxide. The surface layer is made of a material having a resistance value of medium resistance 10 ² to 10 ¹⁰ Ω. For example, nylon, polyamide, polyimide, polyurethane, polyester, silicon, Teflon (registered trademark), polyacetylene, polypyrrole, polytheophene, polycarbonate, polyvinyl, etc. can be used as the resin, but fluorine is used to increase the contact angle with water. It is preferable to use a series resin. Examples of the fluorine-based resin include polyvinylidene fluoride, polyvinyl fluoride, vinylidene fluoride-tetrafluoroethylene copolymer, and vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer.
Furthermore, for the purpose of adjusting to a medium resistance, a conductive material such as carbon black, graphite, titanium oxide, zinc oxide, tin oxide, or iron oxide may be added as appropriate.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

<Evaluation methods>
(Gas resistance)
Gas resistance was evaluated in the following manner. O. D. The applied duty (Duty) was adjusted so that (Optical Density) was in the range of 0.9 to 1.1, and printing was performed using a full-color printer Ipsio CX3000 (manufactured by Ricoh).
Using the ozone weather meter OMS-H type (trade name, manufactured by Suga Test Instruments Co., Ltd.), the obtained printed matter is converted to ozone for 3 hours under the conditions of an ozone concentration of 200 ppm, 24 ° C. and a relative humidity of 60% RH. Exposed.
O. of each printed material after exposure. D. Was measured using a densitometer (Spectrolino: manufactured by Gretag), and an optical density residual ratio (ROD) was determined by the following formula (1). Measurement conditions were such that Red was used for the filter, the light source was D50, and the viewing angle was 2 degrees.

(Where D is the OD value after the exposure test, and D0 is the OD value before the exposure test)

The evaluation criteria are shown below.
◎: ROD is 90% or more ○: ROD is 80% or more and less than 90% △: ROD is 70% or more and less than 80% ×: ROD is less than 70%

(saturation)
The saturation can be calculated from the L * a * b * color space diagram by the following equation (2).

However, in the above formula (2), a * and b * represent the values of the a * coordinate and b * coordinate, respectively, and L * represents the lightness coordinate.
An image in which the toner adhesion amount was changed in the range of 0.1 to 1.0 mg / cm ² on the transfer paper was formed, and the color difference meter “CM-2002” (manufactured by Minolta Co., Ltd.) was used. * b * The space was measured, the saturation C * was calculated according to the above formula (2), and the saturation of the image when the maximum dye adhesion amount was evaluated in the evaluation of the toner adhesion amount in (2) was obtained. .
The evaluation criteria are shown below.
◎: C * is 85 or more ○: C * is 80 or more and 85 or less Δ: C * is 75 or more and 80 or less ×: C * is less than 75

<Examples of resin production>
<Synthesis of polyester>
(Polyester 1) 553 parts of bisphenol A ethylene oxide 2-mole adduct, 196 parts of bisphenol A propylene oxide 2-mole adduct, 220 parts of terephthalic acid, adipic acid in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe 45 parts and 2 parts of dibutyltin oxide were added, reacted for 8 hours at 230 ° C. under normal pressure, and further reacted for 5 hours under reduced pressure of 10 to 15 mmHg. Then, 46 parts of trimellitic anhydride was added to the reaction vessel, and 180 ° C. Reaction was performed at normal pressure for 2 hours to obtain [Polyester 1]. [Polyester 1] had a number average molecular weight of 220, a weight average molecular weight of 5600, a Tg of 43 ° C., and an acid value of 13.

<Synthesis of prepolymer>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

<Preparation of master batch>
Carbon black (Cabot Corp. Regal 400R): 40 parts, Binder resin: Polyester resin (Sanyo Kasei RS-801, acid value 10, Mw 20000, Tg 64 ° C.): 60 parts, water: 30 parts are mixed in a Henschel mixer, A mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 1].

<Production example of colorless transparent toner 1>
<Preparation of WAX dispersion (oil phase)>
In a container equipped with a stir bar and a thermometer, 378 parts of [Polyester 1], 120 parts of paraffin wax (HNP9), release agent (WAX) dispersant (styrene-polyethylene polymer: Tg 73 ° C., number average molecular weight 7100) 96 parts (Releasing agent ratio 80%), 1450 parts of ethyl acetate were added, the temperature was raised to 80 ° C. with stirring, the temperature was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of ethyl acetate was charged into the container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1500 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed is 1 kg / hr, disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 655 parts of a 65% ethyl acetate solution of [Polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [WAX Dispersion 1]. Ethyl acetate was added and adjusted so that the solid content concentration of [WAX dispersion 1] (130 ° C., 30 minutes) was 50%.

<Preparation of aqueous phase>
953 parts of ion-exchanged water, 88 parts of a 25 wt% aqueous dispersion of organic resin fine particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) for dispersion stabilization, dodecyl diphenyl ether 80 parts of a 48.5% aqueous solution of sodium disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 113 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This is designated as [Aqueous Phase 1].

<Emulsification process>
[WAX Dispersion 1] 967 parts, 5% by mass of Clayton APA (manufactured by Southern Clay Products) (in terms of toner solid content) was added, 6 parts of isophoronediamine as amines, and 5, After mixing for 1 minute at 000 rpm, add 137 parts of [Prepolymer 1] and mix for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika), then add 1200 parts of [Aqueous Phase 1] and add TK. The mixture was mixed with a homomixer for 20 minutes while adjusting at a rotation speed of 8,000 to 13,000 rpm to obtain [Emulsion slurry 1].

<Desolvent>
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Dispersion slurry 1].

<Washing->Drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh having a mesh size of 75 μm to obtain [Toner Base 1]. The volume average particle diameter (Dv) was 5.8 μm, the number average particle diameter (Dp) was 5.2 μm, Dv / Dp was 1.12, the average circularity was 0.973, and the ATR value was 0.04. . Next, 1.5 parts of hydrophobic silica H2000 / 4 (particle size: 12 nm, manufactured by Clariant) and 0.5 parts of hydrophobic silica RX50 (particle size: 40 nm, manufactured by Nippon Aerosil Co., Ltd.) were added to 100 parts of the base toner. To obtain [Colorless and transparent toner 1] of the present invention.

(Production example of colorless and transparent toners 2 to 4)
Clayton APA (manufactured by Southern Clay Products) 5 mass% (in terms of toner solid content) of the above-described method for producing colorless transparent toner 1 was changed in the same manner as in Table 1 to obtain colorless and transparent toners 2 to 4 .

<Example of production of black toner 1>
<Preparation of pigment / WAX dispersion (oil phase)>
In a container equipped with a stir bar and a thermometer, 378 parts of [Polyester 1], 120 parts of paraffin wax (HNP9), release agent (WAX) dispersant (styrene-polyethylene polymer: Tg 73 ° C., number average molecular weight 7100) 96 parts (Releasing agent ratio 80%), 1450 parts of ethyl acetate were added, the temperature was raised to 80 ° C. with stirring, the temperature was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 2].
[Raw material solution 2] 1500 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 655 parts of a 65% ethyl acetate solution of [Polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. It was adjusted by adding ethyl acetate so that the solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

<Preparation of aqueous phase>
953 parts of ion-exchanged water, 88 parts of a 25 wt% aqueous dispersion of organic resin fine particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) for dispersion stabilization, dodecyl diphenyl ether 80 parts of a 48.5% aqueous solution of sodium disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 113 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This is designated as [Aqueous Phase 1].

<Emulsification process>
[Pigment / WAX Dispersion 1] 967 parts, 5% by mass of Clayton APA (manufactured by Southern Clay Products) (in terms of toner solid content), 6 parts of isophorone diamine as amines, TK homomixer (manufactured by Special Machine) After mixing for 1 minute at 5,000 rpm, add 137 parts of [Prepolymer 1] and mix for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika), then add 1200 parts of [Aqueous Phase 1]. The mixture was mixed with a TK homomixer at a rotational speed of 8,000 to 13,000 rpm for 20 minutes to obtain [Emulsion slurry 2].

<Desolvent>
[Emulsion slurry 2] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Dispersion slurry 2].

<Washing → Drying>
[Dispersion slurry 2] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filtered Cake 2].
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh of 75 μm to obtain [Toner base 2]. The volume average particle diameter (Dv) was 5.8 μm, the number average particle diameter (Dp) was 5.2 μm, Dv / Dp was 1.12, the average circularity was 0.973, and the ATR value was 0.04. . Next, 1.5 parts of hydrophobic silica H2000 / 4 (particle size: 12 nm, manufactured by Clariant) and 0.5 parts of hydrophobic silica RX50 (particle size: 40 nm, manufactured by Nippon Aerosil Co., Ltd.) were added to 100 parts of the base toner. To obtain [Black Toner 1] of the present invention.

<Production example of magenta toner 1>
[Magenta toner 1] was obtained in the same manner except that the carbon black of the black toner 1 was changed to Solvent Red 49 (oil-soluble dye, Oil Pink 312 manufactured by Orient Chemical Co., Ltd.).

<Production example of magenta toner 2>
[Magenta Toner 2] was obtained in the same manner as in the above magenta toner 1 except that Clayton APA was not added.

<Production example of cyan toner 1>
[Cyan Toner 1] was obtained in the same manner except that the carbon black of the above black toner 1 was changed to 15 parts by weight of Solvent Blue 70 (an oil-soluble dye manufactured by Taoka Chemical Co., Ltd., Oleosol Fast Blue ELN).

<Example of production of yellow toner 1>
[Yellow toner 1] was obtained in the same manner except that the carbon black of the black toner 1 was changed to 15 parts by weight of Disperse Yellow 160 (dispersion dye manufactured by Arimoto Chemical Co., Ltd., Plast Yellow 8050).

<Production Example of Colorless Transparent Toner 5>
(Preparation of first binder resin A1)
As polyol, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 2210 g, terephthalic acid 850 g, 1,2,4-benzenetricarboxylic anhydride 120 g and dibutyltin oxide 0 as esterification catalyst .5 g was put into a 5 liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a downflow condenser and a nitrogen inlet tube, and the temperature was raised to 230 ° C. in a nitrogen atmosphere in a mantle heater to conduct the condensation polymerization reaction. It was. The degree of polymerization was tracked by the softening temperature measured using a constant load extrusion capillary rheometer, and when the desired softening temperature was reached, the reaction was terminated to obtain Resin A1.
Resin A1 had a number average molecular weight of 3502, a weight average molecular weight of 13756, a glass transition temperature of 64.6 ° C., and a resin softening temperature of 115 ° C.

(Preparation of second binder resin B1)
As a polyol, 1230 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 290 g of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, isododecenyl 5 liters equipped with 250 g of succinic anhydride, 310 g of terephthalic acid, 180 g of 1,2,4-benzenetricarboxylic anhydride and 7 g of dibutyltin oxide as an esterification catalyst, equipped with a thermometer, a stainless steel stirrer, a falling condenser and a nitrogen inlet tube The mixture was placed in a four-necked flask and heated to 230 ° C. in a mantle heater under a nitrogen atmosphere to cause a condensation polymerization reaction. The degree of polymerization was monitored by the softening temperature measured using a constant load extrusion capillary rheometer, and when the desired softening temperature was reached, the reaction was terminated to obtain Resin B1. The number average molecular weight was 2778, the weight average molecular weight was 57640, the glass transition temperature was 65.0 ° C., and the resin softening temperature was 138 ° C.

(Create toner particles)
(1-Premix)
60 parts of the first binder resin A1, 40 parts of the second binder resin B1, Clayton APA (manufactured by Southern Clay Products) 5 mass% (in terms of toner solid content) as a release agent, WEP-5 (NOF Corporation) 4.0 parts by weight was added and mixed well with a Henschel mixer.
(2-kneading)
A mortar-type kneader (corroded mill), supply amount 95 kg / h, screw rotation speed 85 rpm, control temperature: supply part (F) 10 ° C., barrel part (K1 to K4) 125 ° C., vent part (V), The die parts (D) were respectively set to 100 ° C. and melt kneaded. The obtained kneaded product was rolled to a thickness of 2 mm with a cooling press roller, cooled with a cooling belt, and then roughly pulverized with a feather mill.
(3-ground classification, external addition)
Then, after pulverizing with a mechanical pulverizer (KTM: Kawasaki Heavy Industries, Ltd.) to an average particle size of 10-12 μm, and further pulverizing with a jet pulverizer (IDS: Nippon Pneumatic Co., Ltd.) while classifying coarse particles. Then, fine powder classification was performed using a rotor type classifier (Teplex type classifier type: 100ATP: manufactured by Hosokawa Micron Corporation) to obtain colored resin particles 1 having a volume average particle size of 9.0 μm. A desired amount (parts by mass) of TS 530 manufactured by Cabogil, which is inorganic fine particles, was added to 100 parts by mass of the colored resin particles 1 and mixed with a Henschel mixer to obtain [colorless transparent toner 5].

<Production Example of Colorless Transparent Toner 6>
A colorless and transparent toner 6 was obtained in the same manner as in the preparation method of <Colorless and transparent toner 5> (1-Premixing) except that Kraton APA was not added.

  A two-component developer prepared by mixing and stirring 5 parts of [Magenta 1] and 95 parts of a silicone resin coated carrier into a magenta toner developing unit of Ipsio CX3000 (manufactured by Ricoh), and developing a yellow toner developing unit and a black toner A two-component developer prepared by mixing and stirring 5 parts of [Colorless and transparent toner 1] and 95 parts of a silicone resin coated carrier is put in the developing unit, and the transfer paper (Ricoh type) without toner in the cyan toner developing unit. 6200Y) and image evaluation was performed. The evaluation results are summarized in Table 2.

[Examples 2-11, Comparative Examples 1-4]
Evaluation was performed in the same manner as in Example 1 except that the development unit, toner and printing paper were changed to those shown in Table 2. The evaluation results are summarized in Table 2.

  The toner accommodated in the cartridge is developed in the order of Y → M → C → K, and the toner image accommodated in the K cartridge is formed on the intermediate transfer member, and the toner image accommodated in the Y cartridge. Is formed at the bottom. The toner superimposed on the intermediate transfer member is transferred from the intermediate transfer member to the recording medium. On the final paper, the toner from the K cartridge is the lowermost layer, and the toner from the Y cartridge is the uppermost layer.

DESCRIPTION OF SYMBOLS 100 Toner 101 Toner storage chamber 102 Toner supply chamber 103 Developing roller 104 Layer control member 105 Supply roller 106 Toner stirring member 107 Opening 108 Sealing seal 201 Process cartridge unit 202 Photosensitive drum 203 Charging roller 204 Developing device 205 Cleaning means 206 Exposure Means 207 Intermediate transfer belt 208 Primary transfer roller 209 Secondary transfer roller 210 Paper

JP 2004-20851 A JP 2006-209090 A Japanese Patent No. 3526629

Claims (7)

  A colorless and transparent toner comprising at least a binder resin and a layered inorganic mineral, wherein the layered inorganic mineral is an organically modified layered inorganic mineral in which at least some of the ions between layers are modified with organic ions Transparent toner.   2. The colorless and transparent toner according to claim 1, wherein the content of the layered inorganic mineral is 0.01 wt% or more and 20 wt% or less. A toner kit including a colored toner and a colorless transparent toner,
The toner kit according to claim 1, wherein the colored toner includes at least a binder resin and a colorant, and the colorless and transparent toner is the colorless and transparent toner according to claim 1. The toner kit according to claim 3, wherein the colorant of the colored toner is a dye. A toner kit having a plurality of developer containers, a developer supply member that supplies developer to the surface of the developer carrier from each developer container of the toner kit, and a developer that supports the supplied developer on the surface A developing device having a carrier,
The developing device according to claim 3, wherein the toner kit is the toner kit according to claim 3. In an image forming apparatus having at least toner image forming means for forming a color toner image and colorless transparent toner on a recording medium and fixing means for fixing the toner image on the recording medium to the recording medium.
A latent image carrier on which the toner image forming means carries a latent image;
Charging means for uniformly charging the surface of the latent image carrier;
Exposure means for exposing the surface of the charged latent image carrier on the basis of image data and writing an electrostatic latent image;
A developing device that supplies toner to the electrostatic latent image formed on the surface of the latent image carrier to visualize it;
Transfer means for transferring a visible image on the surface of the latent image carrier to a recording medium;
An image forming apparatus using the developing device according to claim 5 as the developing device.   At least a toner image forming step for forming an image made of colored toner and an image made of a colorless transparent toner on the recording medium, and a fixing step for fixing the toner image on the recording medium formed in the toner image forming step to the recording medium. An image forming method, wherein the toner kit according to claim 3 or 4 is used as toner.

Images